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1.
In the search of a useful method for determining excess enthalpies as a function of temperature Calvet calorimetry was employed. To this end, excess molar enthalpies
at 298.15 and 333.15 K and excess molar heat capacities
within 283.15–333.15 K were determined for the 1-decanol+n-decane system over the whole composition range. An isothermal flow Calvet-type calorimeter was used for
measurements, whereas
were determined by means of a Setaram Micro DSC calorimeter. Excess enthalpies within 283.15–333.15 K were indirectly obtained through the integration of
(T) data using
at 298.15 K. The results obtained at 333.15 K agreed with those determined directly, implying the thermodynamic consistency of the measured data and, therefore, the reliability of the indirect method.  相似文献   

2.
In this work some calorimetric measurements were also carried out on the electrorefining silver by using different current densities with a Calvet type microcalorimeter at room temperature. The ratio (R) of the measured heat (
m) to the input electric energy (
in) and the excess heat (
ex), i.e., difference between
m and
in during the electrorefining process, were discussed in terms of general thermodynamics. It was found that the R and
ex for silver were related with the current density or cell voltage employed in the experiment. The results obtained here also indicate that the heat generation under different conditions, such as different currents or voltages may be caused partially by the irreversibility of the process or by some unknown processes.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

3.
Enthalpic relaxation has been used to model the development of the glass transition in polymers, using kinetic parameters determined separately. For this purpose the Kohlrausch-Williams-Watt stretched exponential function, relating the extent of relaxation, Φ(t), to time t and an average relaxation time, τa, i.e.
where β is inversely related to the breadth of the relaxation spectrum, has been adopted. The relaxation time dependence on temperature was taken to follow the modified Arrhenius relationship,
where T is the storage and T′ the fictive temperature, X is the structure factor and ΔH the activation enthalpy. Both have been found to describe the process of enthalpic relaxation in polymer glasses and a direct comparison has been made with the change in specific heat observed with different cooling rates in DSC experiments. The effect of variables, such as activation enthalpies, pre-exponential factors, and the non-linear factors such as X and β on the observed Tgs and the temperature range over which the transition occurred have been determined. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

4.
The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation
and that for the latter 50% mass-loss of HNNC described by the reaction equations
and
This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

5.
The example of the sequence of reactions
and the steady-state approximation are used to present a demonstration of the fact that the evolution of the reaction rates under non-isothermal conditions depends on the ratio of the activation energies and on the heating rate. At the same time, it is shown that, under isothermal conditions, the ratio of the activation energies plays no role. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

6.
We have investigated effects of shear flow on the structure of lamellar phase in hepta(oxyethylene glycol)—n—hexadecylether—water system using small-angle neutron scattering (SANS) under shear flow at the shear rates (
) from 10–3 s–1 to 50 s–1. In the range
=10–2 ~1 s–1, significant changes have been observed in both intensity and position of the reflection peak. Small-angle X-ray scattering without shear has been also measured at various concentrations and temperatures. It has been suggested from these results that the shear flow causes contraction of lamellar domains and formation of a new domain composed of disrupted bilayers which grows rapidly with increasing shear rate and reconstructs original microstructures.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

7.
A new approximation is proposed to the integral of the Boltzmann factor:
  相似文献   

8.
The kinetics of the reactions of ClO3 with HSO3 and H2SO3 was studied by measuring the concentration of [Cl] and [H+] both in chlorate-bisulfite and chlorate-sulfite/bisulfite solutions. A reaction mechanism was applied for simulation of the experimental observations. Rate constants k1 = (1±0.5)·10−4 M−1 s−1 and k2 = (0.23±0.01) M−1 s−1 were determined for the following reactions:
((1))
((2))
Rate constant k1 was obtained directly from the experimental results of chloratesulfite/ bisulfite reactions, where reaction (1) is predominant. Rate constant k2 was obtained by computer fitting of [Cl] and [H+] to the experimental values both in chlorate-bisulfite and chlorate-sulfite/bisulfite reactions.  相似文献   

9.
The low-pressure discharge flow technique with resonance fluorescence monitoring of OH has been applied to study the kinetics of the overall reaction:
(1)
The rate constant of k 1 = (1.09 ± 0.09(1σ)) × 10−12 cm3 molecule−1 s−1 has been determined at T = 297 ± 3 K. This value agrees well with the IUPAC recommendation which is based on photolysis kinetic studies.  相似文献   

10.
The energy E(G) of a graph G is defined as the sum of the absolute values of all the eigenvalues of the adjacency matrix of the graph G. This quantity is used in chemistry to approximate the total π-electron energy of molecules and in particular, in case G is bipartite, alternant hydrocarbons. In this paper, we show that if G = (V 1, V 2; E) is a bipartite graph with edges and , then
and
must hold.   相似文献   

11.
The solubility of boric acid [B] in LiCl, NaCl, KCl, RbCl, and CsCl was determined as a function of ionic strength (0–6 mol ⋅ kg−1) at 25 C. The results were examined using the Pitzer equation
where [B]0 is the concentration of boric acid in water and [B] in solution, γB is the activity coefficient, νi is the number of ions (i), λBc, λBa are parameters related to the interaction of boric acid with cation c and anion a, ζB-a−c is related to the interaction of boric acid with both cation and anion and m is the salt molality. The literature values for the solubility of boric acid in a number of other electrolytes were also examined using the same equation. The results for the 2νcλBc+2νaλBa term (equal to the salting coefficient k S) were examined in terms of the ionic interactions in the solutions. The solubility of boric acid in LiCl, NaCl, and KCl solutions is not a strong function of temperature and the results can be used over a limited temperature range (5–35 C). Boric acid is soluble in the order SO4 > NO3 and F > Cl > Br > I in common cation solutions. In common anion salt solutions, the order is Cs > Rb > K > Na > Li > H and Ba > Sr > Ca > Mg. The results were examined using correlations of k S with the volume properties of the ions. When direct measurements were not available, k S and ζB-c−a were estimated from known values of λBc and λBa.The values of λBc, λBa, and ζB-a−c can be used to estimate the boric acid activity coefficients γB and solubility [B] in natural mixed electrolyte solutions (seawater and brines) using the more general Pitzer equation
  相似文献   

12.
The thermal decomposition of zirconium oxyhydroxides prepared by the mixture of aqueous zirconium oxychloride solutions and aqueous solutions of sodium hydroxide or ammonium hydroxide under various conditions has been examined by thermogravimetry, differential thermal analysis, X-ray diffraction study and infrared spectrophotometry. As a result, it is seen that the thermal decomposition of zirconium oxyhydroxide, in which the composition is ZrO2-x(OH)2xyH2O where x2 and 1y<2, proceeds according to the following process:
This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

13.
Emanation thermal analysis (ETA), thermogravimetry and high temperature XRD were used to characterize the thermal behavior during dehydration of natural Na montmorillonite (Upton Wyoming, USA) and homoionic montmorillonite (MMT) samples saturated with different cations, i.e. Li+, Cs+, NH4+, Mg2+ and Al3+. ETA results characterized radon mobility and microstructure changes that accompanied the mass loss of the samples due to dehydration on heating in air. A collapse of interlayer space between the silicate sheets after water release from the MMT samples was characterized by a decrease of the radon release rate, ΔE. Decreases in c-axis basal spacing (d 001) values determined from XRD patterns for the different montmorillonite samples follow the sequence:
The decrease of the radon release rate (ΔE) determined by ETA that characterized microstructure changes due to collapse of interlayer space corresponded well to differences in the c-axis basal spacing (Δd 001) values determined from the XRD patterns before and after samples dehydration.  相似文献   

14.
The narcissus constant, N = 2.3983843828..., is defined as a number that fulfills the narcissistic infinite nested radical equation
Incorporation of this constant, its square and its cube into the generalized version of the Lennard-Jones potential function gives the narcissus constant potential function
which (a) is suitable for modeling van der Waals interaction due to its agreement with the Lennard-Jones (12-6) potential energy curve over long range, and (b) forms simple generalized hybrid interatomic–intermolecular potential energy function due to its correlation with the averaged form of Lennard-Jones, Morse, Buckingham and Linnett potential energy curve near the minimum well-depth.   相似文献   

15.
The theory of the polarographic catalytic currents (mechanism CE) has been developed for the system: Ni2+-L-Xp− where L: pyridine (Py), nicotinamide (NA), N,N-diethylnicotinamide (DEN), nicotine (NC) and Xp−: NO 3, AcO, HPO2− 4 . The theory is based on the kinetic parallel heterogeneous catalytic reactions:
(1a)
(1b)
with the use of Langmuir’s adsorbed isotherm. The kinetic equations obtained for average and instantaneous currents allowed to determine the Langmuir’s parameters (NA<DEN<NC), kinetic parameters and the contribution of reactions 1a and b to the summary catalytic currents. The k h value rises with the increase of the NiX2−p stability constant. The correlation k hk h was explained by the additional effect of the field electrode through Xp−. These effects base the reaction 1b instead of accepted early alternative reaction of the ligand exchange. In spite of the fact that k hk h, the contribution of the reaction 1a in the summary catalytic current attained more than 60% (Py, DEN) due to the influence of the ψ0 potential. Dedicated to Professor Zbigniew Galus on the occasion of his 70th birthday and in recognition of his many contributions to electrochemistry  相似文献   

16.
Structural and thermal properties of the 20Li2O-80TeO2 glass were studied using X-ray diffraction analysis and differential scanning calorimetry techniques to understand and control the crystallization process on this glass. The γ-TeO2, α-TeO2 and α-Li2Te2O5 phases were identified during the crystallization in this glass. Activation energies and Avrami exponent n were calculated from non-isothermal measurements for glasses with different particle size. The mean values of Avrami exponent were obtained for glasses with 63–75 and 45–63 μm particle sizes such as , but glasses with particle size 38–45 μm and smaller than 38 g,m presented .  相似文献   

17.
For getting an insight into the mechanism of atmospheric autoxidation of sulfur(IV), the kinetics of this autoxidation reaction catalyzed by CoO, Co2O3 and Ni2O3 in buffered alkaline medium has been studied, and found to be defined by Eqs. I and II for catalysis by cobalt oxides and Ni2O3, respectively.
(I)
(II)
The values of empirical rate parameters were: A{0.22(CoO), 0.8 L mol−1s−1 (Co2O3)}, K 1{2.5 × 102 (Ni2O3)}, K 2{2.5 × 102(CoO), 0.6 × 102 (Co2O3)} and k 1{5.0 × 10−2(Ni2O3), 1.0 × 10−6(CoO), 1.7 × 10−5 s−1(Co2O3)} at pH 8.20 (CoO and Co2O3) and pH 7.05 (Ni2O3) and 30 °C. This is perhaps the first study in which the detailed kinetics in the presence of ethanol, a well known free radical scavenger for oxysulfur radicals, has been carried out, and the rate laws for catalysis by cobalt oxides and Ni2O3 in the presence of ethanol were Eqs. III and IV, respectively.
(III)
(IV)
For comparison, the effect of ethanol on these catalytic reactions was studied in acidic medium also. In addition, alkaline medium, the values of the inhibition factor C were 1.9 × 104 and 4.0 × 10L mol−1 s for CoO and Co2O3, respectively; for Ni2O3, C was only 3.0 × 102 only. On the other hand, in acidic medium, the values of this factor were all low: 20 (CoO), 0.7 (Co2O3) and 1.4 (Ni2O3). Based on these results, a radical mechanism for CoO and Co2O3 catalysis in alkaline medium, and a nonradical mechanism for Ni2O3 in both alkaline and acidic media and for cobalt oxides in acidic media are proposed.  相似文献   

18.
The kinetics of catalytic decomposition of NO over Cu/ZSM-5 catalyst has been studied in an integral flow reactor at atmospheric pressure. Kinetic analysis is based on the assumption that the surface reaction represents the rate-determining step. On the basis of theoretical considerations of different interactions between reactants and catalyst, and experimental evidences, three different mechanistic kinetic models were chosen. Also a power-law model was tested. The best agreement has been achieved with the model
  相似文献   

19.
A u.v.–vis spectrophotometric study of the adduct formation of the nickel(II) Schiff base complexes,([NiL]) where L = [3-methoxysalophen, N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediimine] (1), [4-methoxysalophen, N,N′-bis(4-methoxysalicylidene)-1,2-phenylenediimine] (2), [5-methoxysalophen, N,N′-bis(5-methoxysalicylidene)-1,2-phenylenediimine] (3) and [Salophen, [N,N′-bis(salicylaldehydo)-1,2-phenylenediimine] (4) as donors with R2SnCl2 (R = methyl, phenyl and n-butyl) as acceptors have been investigated in chloroform, as solvent. Adducts have been characterized by 1H, 13C and 119Sn NMR, IR and electronic spectroscopy and CHN elemental microanalysis. The formation constants and the thermodynamic free energies were measured using u.v.–vis spectrophotometry titration for 1:1 adduct formation at various temperatures (T = 278 to 308 K). The trend of the adduct formation of the nickel Schiff base complexes with a given tin acceptor decreases as follows:
and
The trend of the reaction of R2SnCl2 acceptors toward a given nickel Schiff base complex is as follows:
  相似文献   

20.
The solubility of siderite (FeCO3) at 25°C under constant CO2 partial pressure [p(CO2)] was determined in NaCl solutions as a function of ionic strength. The dissolution of FeCO3(s) for the reaction
has been determined as a function of pH = – log[H+]. From these values we have determined the equilibrium constant for the stoichiometric solubility to FeCO3(s) in NaCl
These values have been fitted to the equation
with a standard error of s = 0.15. The extrapolated value of log(K o sp) – 10.9 in water is in good agreement with data in the literature (– 10.8 to – 11.2) determined in solutions of different composition and ionic strength.The measured values of the activity coefficient, T(Fe2+) T(CO3 2–), have been used to estimate the stability constant for the formation of the FeCO3 ion pair, K*(FeCO3). The values of K*(FeCO3) have been fitted to the equation (s = 0.09)
The value of log[K o(FeCO3)] in water found in this study (6.3 ± 0.2) is slightly higher than the value found from extrapolations in 1.0 m NaClO4 solutions (5.9 ± 0.2). These differences are related to the model used to determine the activity coefficients of the Fe(II) and carbonate species in the two solutions.  相似文献   

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